WO2016021892A1 - Thermoelectric element, manufacturing method thereof and device containing thermal element - Google Patents

Abstract

Provided are a thermoelectric element, a manufacturing method thereof, and a device containing a thermoelectric element, the thermoelectric element comprising: a plurality of lower electrodes; first electrolyte cells which are arranged on individual tops of the lower electrodes, contain first electrolytes having positive thermal coefficients in which a reduction reaction is caused by temperature rise of the lower electrodes, and are connected to first electrolyte channels which have an inlet and an outlet arranged at both ends thereof and which receive the first electrolytes; second electrolyte cells which are individually arranged to be spaced apart from the fist electrolyte cells on a single lower electrode, contain second electrolytes having negative thermal coefficients in which an oxidation reaction is caused by temperature rise of the lower electrode, and are connected to second electrolyte channels which have an inlet and an outlet arranged at both ends thereof and which receive the second electrolytes; and a plurality of upper electrodes which are arranged on the first electrolyte cells and the second electrolyte cells so as to be connected to the first electrolyte cells and the second electrolyte cells arranged on different lower electrodes.

Description

Thermoelectric element, method for manufacturing the same, and apparatus including thermoelectric element

The present invention relates to a thermoelectric element, a method for manufacturing the same, and a device including a thermoelectric element, and more particularly, a thermoelectric element for converting thermo-electric energy into a temperature difference between two ends by using a thermoelectric electrolyte, a method for manufacturing the same, and a thermoelectric element. It relates to a device comprising a.

Thermoelectric element is a device using the thermoelectric effect represented by the interaction of heat and electricity, a device using the Seebeck effect that generates electrical energy by the temperature difference, a Peltier device using a phenomenon that the absorption / generation of heat by the applied electrical energy occurs There is this. Thermoelectric devices are widely used in a wide range of industries such as space, aviation, semiconductors, and power generation.

Recently, various efforts to develop alternative energy and to improve energy efficiency to solve energy problems are active worldwide. As part of this, the thermoelectric element technology that collects waste heat and converts it into electrical energy has been attracting attention. Thermocouples, also known as thermogalvanic cells or thermal electrochemical cells, are power generation mechanisms based on the temperature dependence of the electrochemical redox potential of the electrolyte, direct conversion of thermo-electric energy, simple components, It has the advantages of semi-permanent durability, low maintenance cost and no carbon emissions. Therefore, the thermal cell technology is reported as the most effective coping technology for waste heat energy recovery. In particular, since it has the advantage of efficiently absorbing the waste heat of less than 100 ℃ based on the mechanical flexibility and low production cost, researches for improving the efficiency of thermoelectric elements using thermoelectric electrolytes have recently been actively replaced by solid state thermoelectric elements. .

One object of the present invention is to provide a thermoelectric device having a high output voltage and high power output.

Another object of the present invention is to provide a method of manufacturing a thermoelectric element.

Still another object of the present invention is to provide an apparatus including the thermoelectric element.

In one aspect, a thermoelectric device for one purpose of the present invention includes a plurality of lower electrodes, first electrolytic cells, second electrolytic cells and a plurality of upper electrodes.

The first electrolytic cells are disposed above each of the lower electrodes, and include a first electrolyte having a positive thermoelectric coefficient in which a reduction reaction occurs due to an increase in temperature of the lower electrode, and an inlet and an outlet are disposed at both ends thereof. And a first electrolyte channel containing a first electrolyte. The second electrolytic cells each include a second electrolyte having a negative thermoelectric coefficient disposed on one lower electrode and spaced apart from the first electrolytic cell and in which an oxidation reaction occurs due to an increase in temperature of the lower electrode. Disposed at both ends and connected to a second electrolyte channel containing the second electrolyte. The upper electrodes are disposed on the first and second electrolytic cells so as to be connected to the first electrolytic cell and the second electrolytic cell disposed on different lower electrodes.

In one embodiment, the first electrolytic cells are connected in a one-to-one correspondence with a plurality of first electrolyte channels each having an inlet and an outlet, and the second electrolytic cells are independent of each other having an inlet and an outlet. It can be connected in a one-to-one correspondence with a plurality of second electrolyte channels.

In one embodiment, the first electrolytic cells may be connected in series between the inlet and outlet of the first electrolyte channel, and the second electrolytic cells may be connected in series between the inlet and outlet of the second electrolyte channel.

In an embodiment, the first electrolytic cell and the second electrolytic cell are alternately arranged in the first direction, and the first electrolytic cell and the second electrolytic cell are alternately arranged in the second direction crossing the first direction. The first electrolyte channels are sequentially connected to the first electrolytic cells included in the xth row group (where x is a natural number), which is any one row group arranged in a row, in the first direction, and the x The first electrolytic cells of the x + 1 row group arranged in the second direction of the row group are sequentially connected in a direction opposite to the first direction, and the x row group and the x + 1 row group are corresponding row groups The first first electrolytic cells in E or the last first electrolytic cells in the row group are connected to each other, and the second electrolyte channel is included in the x row group, which is any one row group arranged in a row. The second electrolytic cells are sequentially connected in the first direction, and the xth row The second electrolytic cells of the x + 1 row group arranged in the second direction of the group are sequentially connected in the opposite direction to the first direction, and the xth row group and the x + 1 row group are arranged in the corresponding row group. The first second electrolytic cells of or the last second electrolytic cells in the row group may be connected to each other.

In an embodiment, the first electrolytic cell and the second electrolytic cell are alternately arranged in the first direction, and the first electrolytic cell and the second electrolytic cell are alternately arranged in the second direction crossing the first direction. The first electrolytic cell and any one of the first electrolytic cells of the y + 1 column group included in the y th column group, wherein y is a natural number, The second electrolytic cell of any one of the y-th column groups, which is connected to each other in the second direction by a first electrolyte channel, and the plurality of first electrolyte channels are separated from each other and arranged in a row. Any one of the second electrolytic cells of the y + 1 column group is connected to each other in the second direction by a second electrolyte channel, and the plurality of second electrolyte channels may be independently separated from each other.

In one embodiment, the first electrolytic cells may be connected in series between the inlet and outlet of the first electrolyte channel, and the second electrolytic cells may be connected in series between the inlet and outlet of the second electrolyte channel.

In one embodiment, the first electrolyte channel includes the first electrolytic cell and the x + 1 row group in the y th column of the x th row group (where x represents a natural number), which is any one row group arranged in a row. The first electrolytic cells of the y + 1th column are connected, and the second electrolyte channel is the second electrolytic cell of the yth column of the xth row group and the x + 1st row group of any one row group arranged in a row. The second electrolytic cells of the y + 1 column may be connected.

In one embodiment, the second electrolytic cell of the last column of the first row group may be connected to the second electrolyte channel alone, and the first electrolytic cell of the first column of the last row group may be connected to the first electrolyte channel alone.

In one embodiment, the redox couple contained in the first electrolytic cell is _{Fe 2 (SO 4) 3 /} FeSO 4, I - / I 3-, Np 4 + / NpO 2 +, Pu 4 + / PuO 2 2 ^{+, CN - / CNO -,} NO 2 - / NO 3 -, I - / IO 3 -, ClO 3 - / ClO 4 -, ClO - / ClO 2 - and Cl ^- / ClO ^- is at least one selected from the The redox couple included in the second electrolytic cell is K ₃ Fe (CN) ₆ / K ₄ Fe (CN) ₆ , K ₃ Fe (CN) ₆ / (NH ₄ ) ₄ Fe (CN) _{6 ,} Np ^{3 +} / Np ^{4 +} , Cu ⁺ / Cu ^{2 +} , Fe ^{2 +} / Fe ^{3 +} , PuO ₂ ⁺ / PuO ₂ ²⁺ , Pu ^{3 +} / Pu ^{4 +} , NpO ₂ ⁺ / NpO ₂ ^{2 +} , Tl ⁺ / Tl ³ At least one selected from ⁺ , NH ₄ ⁺ / N ₂ H ₅ ⁺ , NH ₄ ⁺ / NH ₃ OH ⁺ , Mn ^{2 +} / Mn ^{3 +} and Am ³⁺ / Am ⁴⁺ .

The thermoelectric device may further include a barrier rib structure interposed between the lower electrodes and the upper electrodes and separate the first and second electrolytic cells. 2 openings corresponding to the electrolytic cells, at least one opening connected to at least one opening in which the first electrolytic cell is disposed to form a first electrolyte channel, and at least one opening in which the second electrolytic cell is disposed It may include a second electrolyte flow path portion connected to form a second electrolyte channel.

In an embodiment, when a temperature difference occurs between the lower electrodes and the upper electrode, the lower electrode, the first electrolytic cell, the upper electrode, the second electrolytic cell, and any one of the lower electrodes, based on one lower electrode. The electrons may continuously move in the order of other lower electrodes disposed adjacent to the lower electrode.

In one embodiment, the lower electrodes and the upper electrodes are arranged in a row in the first direction within one row, and the upper electrodes are arranged in the second direction crossing the first direction between the different rows so as to be different from each other. The first electrolytic cell and the second electrolytic cell of the first column may be connected to each other, or the first and second electrolytic cells of the last column of different rows may be connected to each other.

In one embodiment, the first electrolyte and the second electrolyte may be in a liquid or gel state.

According to another aspect of the present invention, there is provided a method of manufacturing a thermoelectric device, forming a plurality of lower electrodes disposed in a matrix form on a lower substrate in a first direction and a second direction crossing the first direction. Arranging a partition structure including a plurality of openings, a first electrolyte flow path part, and a second electrolyte flow path part on the lower substrate on which the openings are formed such that two openings among the plurality of openings are located at one lower electrode, Assembling the upper substrate on which the upper electrodes are formed so that the two upper electrodes are disposed on the lower electrode, with the lower substrate and the barrier rib structure, and injecting a first electrolyte solution into the first electrolyte flow path part to form the first electrolyte flow path part. A first electrolyte cell is formed in the opening connected to the second electrolyte cell, and a second electrolyte solution is injected into the second electrolyte flow path part to form the second electrolyte; And forming a second electrolytic cell in the opening connected to the flow path part.

In an embodiment, the forming of the second electrolytic cell may include injecting the first electrolyte solution into one end of the first electrolyte flow path while opening both ends of the first electrolyte flow path, and opening both ends of the second electrolyte flow path. Injecting the second electrolyte solution into one end portion in a state where the first electrolyte solution is filled in an opening connected to the first electrolyte flow passage portion and the first electrolyte flow passage portion. Sealing the other end, and sealing one end and the other end of the second electrolyte flow path part in a state where the second electrolyte solution is filled in the opening connected to the second electrolyte flow path part and the second electrolyte flow path part. It may include a step.

In one embodiment, the openings include first openings connected to each of a plurality of first electrolyte flow path parts independent of each other, and second openings connected to a plurality of second electrolyte flow path parts independent of each other, and the first openings And the second openings may be alternately disposed in the first direction and alternately disposed in the second direction.

In one embodiment, the openings include a plurality of first openings connected to the first electrolyte flow path part and a plurality of second openings connected to the second electrolyte flow path part, and the first openings and the second opening part. They may be alternately arranged in the first direction and alternately arranged in the second direction.

In one embodiment, the barrier rib structure includes at least two or more first electrolyte flow path portions and at least two or more second electrolyte flow passage portions, each of the first electrolyte flow passage portions connecting first openings in the second direction, Each of the second electrolyte flow path parts may connect the second openings in the second direction.

In some embodiments, each of the first electrolyte flow path parts may be independent of each other, and each of the second electrolyte flow path parts may be independent of each other.

An apparatus for still another object of the present invention includes a battery in which the thermoelectric element is formed. In this case, the positive terminal and the negative terminal of the thermoelectric element may be connected to the positive and negative terminals of the battery, respectively.

In one embodiment, a capacitor that stores the power produced in the thermoelectric element, and delivers to the battery may be formed in the battery.

An apparatus for still another object of the present invention includes a battery cover in which the thermoelectric element is formed. In this case, the thermoelectric element may include a positive electrode terminal and a negative electrode terminal that are in contact with the positive electrode and the negative electrode of the battery, respectively, and electrically connected to the lower electrodes and the upper electrodes.

In an embodiment, a capacitor connected to the thermoelectric element to store power generated by the thermoelectric element may be formed in the battery cover, and the capacitor may be provided with a terminal connected to the battery.

An apparatus for still another object of the present invention may be an automotive sunroof window or greenhouse window including the thermoelectric element.

According to the thermoelectric element, the manufacturing method thereof, and the apparatus including the thermoelectric element of the present invention, the thermoelectric element can be operated by the waste heat of 100 degrees C or less, and the output voltage and the power productivity can be improved. The thermoelectric element may be applied to an electronic device to operate by heat generated by the driving of the electronic device to generate electric power, and to be easily used in a window or a greenhouse of an automobile.

As in the present invention, a thermoelectric device including a plurality of electrolytic cells may be easily and simply manufactured by configuring an electrolyte channel connected to the electrolytic cell.

1 is a cross-sectional view illustrating a thermoelectric device according to an exemplary embodiment of the present invention.

2 is a perspective view illustrating a thermoelectric device according to an exemplary embodiment of the present invention.

3 is a cross-sectional view of the thermoelectric element illustrated in FIG. 2.

FIG. 4 is a plan view illustrating electrical connection between unit cells of the thermoelectric element illustrated in FIG. 2.

5 is an enlarged partial plan view of the thermoelectric element of FIG. 4.

FIG. 6 is a graph illustrating a change in open voltage according to the number of unit cells in the thermoelectric element illustrated in FIG. 2.

FIG. 7 is a cross-sectional view for describing a method of manufacturing the thermoelectric element illustrated in FIG. 2.

FIG. 8 is a plan view illustrating a method of manufacturing the thermoelectric element illustrated in FIG. 2.

9 is a plan view illustrating a thermoelectric device according to another exemplary embodiment of the present invention.

FIG. 10 is a plan view illustrating a method of manufacturing the thermoelectric element of FIG. 9.

11 is a plan view illustrating a thermoelectric device according to yet another exemplary embodiment of the present invention.

FIG. 12 is a plan view illustrating a method of manufacturing the thermoelectric element of FIG. 11.

13 is a cross-sectional view illustrating an apparatus including a thermoelectric device according to an exemplary embodiment of the present invention.

FIG. 14 is a diagram for describing a connection relationship between a thermoelectric element and a battery in FIG. 13.

15 to 17 are diagrams for describing an apparatus including a thermoelectric device according to an exemplary embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. As the inventive concept allows for various changes and numerous modifications, particular embodiments will be described in detail. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that a feature, component, or the like described in the specification exists, and one or more other features or components may not be present or added thereto. It does not mean nothing.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

1 is a cross-sectional view illustrating a thermoelectric device according to an exemplary embodiment of the present invention.

Referring to FIG. 1, the thermoelectric element 100 includes two lower electrodes 112 and 114, two electrolytic cells 122 and 124, and one upper electrode 130.

The two lower electrodes 112 and 114 are spaced apart from each other, and the upper electrode 130 is disposed on the lower electrodes 112 and 114, and both ends of the upper electrode 130 are connected to the lower electrodes 112. , 114) respectively.

Specifically, the first electrolytic cell 122 is interposed between the first lower electrode 112 and the first end of the upper electrode 130 among the lower electrodes 112 and 114. The second electrolytic cell 124 is disposed on the second lower electrode 114 spaced apart from the first lower electrode 112, and is disposed between the second lower electrode 114 and the second end of the upper electrode 130. do. The second end is an end opposite to the first end of the upper electrode 130. In this case, the first lower electrode 112 and the second lower electrode 114 may be hot electrodes having a relatively higher temperature than the upper electrode 130, and the upper electrode 130 may be a cold electrode. The surface on which the first and second lower electrodes 112 and 114 are disposed may receive heat from the outside, and the upper electrode 130 may be disposed on an opposite surface thereof.

The first and second lower electrodes 112 and 114 and the upper electrode 130 are formed of a conductive layer. The conductive layer may be formed of a colored metal such as aluminum, copper, or silver, or a transparent metal oxide such as indium tin oxide (ITO). Alternatively, the first and second lower electrodes 112 and 114 and the upper electrode 130 may be formed of a carbon-based material. The carbon-based material is not particularly limited, but when the first and second electrodes 110 and 120 are formed of carbon nanotubes or graphenes, characteristics of the thermoelectric element 100 may be changed. It can be further improved.

The first electrolytic cell 122 is an electrolytic cell including an electrolyte having a positive thermoelectric coefficient in which a reduction reaction occurs due to a temperature rise. At the same time, the second electrolytic cell 124 is an electrolytic cell containing an electrolyte having a negative thermoelectric coefficient in which an oxidation reaction occurs by a temperature rise. Each of the first and second electrolytic cells 122 and 124 may be a liquid or a gel. Since the first electrolytic cell 122 is an electrolytic cell having a positive thermoelectric coefficient, and the second electrolytic cell 124 is an electrolytic cell having a negative thermoelectric coefficient, the movement path of electrons is sequentially performed in the first lower electrode 112. ), The first electrolytic cell 122, the upper electrode 130, the second electrolytic cell 124, and the second lower electrode 114.

For example, a first electrolytic redox couple contained in the cell (122) (redox couple) _{As, Fe 2 (SO 4) 3} / FeSO 4, I - / I 3-, Np 4 + / NpO 2 +, Pu ^{_{4 + / PuO 2 2 +,}} CN - / CNO -, NO 2 - / NO 3 -, I - / IO 3 -, ClO 3 - / ClO 4 -, ClO - / ClO 2 -, Cl - / ClO - , etc. Can be mentioned.

As the redox couple included in the second electrolytic cell 124, K ₃ Fe (CN) ₆ / K ₄ Fe (CN) ₆ , K ₃ Fe (CN) ₆ / (NH ₄ ) ₄ Fe (CN) _6, Np ^{3 +} / Np ^{4 +} , Cu ⁺ / Cu ^{2 +} , Fe ^{2 +} / Fe ^{3 +} , PuO ₂ ⁺ / PuO ₂ ^{2 +} , Pu ^{3 +} / Pu ^{4 +} , NpO ₂ ⁺ / NpO ₂ ²⁺ , Tl ⁺ / Tl ³⁺ , NH ₄ ⁺ / N ₂ H ₅ ⁺ , NH ₄ ⁺ / NH ₃ OH ⁺ , Mn ²⁺ / Mn ³⁺ , Am ³⁺ / Am ⁴⁺ , and the like.

By constructing the first and second electrolytic cells 122 and 124 as described above, since the thermoelectric element 100 can operate even at 100 ° C. or lower, waste heat of living such as body temperature, heat generated by a portable device, etc. are recycled. can do.

For example, the first electrolytic cell 122 includes an electrolyte solution containing ferrous sulfate (FeSO ₄ ) / ferric sulfate (Fe ₂ SO ₄ ) as an electrolyte, and the second electrolytic cell 124 is an erythritis (K) as an electrolyte. ₃ [Fe (CN) ₆ ]) / septic solution (K ₄ [Fe (CN) ₆ ]) may be included.

On the contrary, when the first electrolytic cell 122 and the second electrolytic cell 124 are in a gel state, each of the first electrolytic cell 122 and the second electrolytic cell 124 may have a gel state in addition to the electrolyte. It may further comprise a polymer for maintaining.

In an embodiment, the first electrolytic cell 122 may include iron (Fe) divalent ions and / or iron trivalent ions. That is, only the iron divalent ions or the iron trivalent ions may be present in the first electrolytic cell 122 or the iron divalent ions and the trivalent ions may coexist. In addition, the second electrolytic cell 124 may include hexacyano iron trivalent anion (Fe (CN) ₆ ^{3 −} ) and / or hexacyano iron tetravalent anion (Fe (CN) ₆ ^4- ). . According to the oxidation / reduction reaction of iron ions, only the hexacyano iron trivalent anion or tetravalent anion is present in the second electrolytic cell 124, or the hexacyano iron trivalent anion and the tetravalent anion coexist. Can be.

Specifically, when the temperature of the first and second lower electrodes 112 and 114 rises, iron trivalent ions are reduced to iron divalent ions in the first electrolytic cell 122 by the temperature rise, and the second In the electrolytic cell 124, hexacyano iron tetravalent ions are oxidized to become hexacyano iron trivalent ions. At the same time, in the first electrolytic cell 122 on the side where the upper electrode 130 is disposed, which is relatively low temperature compared to the first and second lower electrodes 112 and 114, the iron divalent ions become iron trivalent. The electrons are transferred to the upper electrode 130 while being oxidized to ions. At this time, a potential difference of about 0.4 to 0.6 mV occurs between the first lower electrode 112 and the upper electrode 130 by the reduction and oxidation of the first electrolytic cell 122. In the second electrolytic cell 124 on the side where the upper electrode 130 is disposed, electrons generated by the oxidation reaction of the first electrolytic cell 122 are received through the upper electrode 130, and the second electrolytic cell 124 is provided. The hexacyano iron trivalent ions of the electrons are reduced to become hexacyano iron tetravalent ions. The hexacyano iron tetravalent ions are oxidized by the temperature rise of the second lower electrode 114 to emit electrons. The electrons may be provided to an external load connected to the second lower electrode 114 through the second lower electrode 114 to generate power. In this case, a potential difference of about 1.4 to 1.6 mV is generated between the upper electrode 130 and the second lower electrode 114 by oxidation and reduction of the second electrolytic cell 124. Accordingly, the thermoelectric coefficient (dV / dT, unit mV / K), which is a voltage change according to the temperature change of the thermoelectric element 100, may be about 1.8 to 2.2 mV / K.

When the overall thermoelectric coefficient of the thermoelectric element 100 is x mV / K, its output voltage may be expressed as in Equation 1 below.

[Equation 1]

Output voltage (mV) = thermoelectric coefficient of thermoelectric element (mV / K) × (T _H -T _C )

In Equation 1, T _H is the temperature of the lower electrodes 112 and 114, T _C means the temperature of the upper electrode 130, the unit of the output voltage is mV, the temperature unit is K. For example, when the first electrolytic cell 122 includes iron ions and the second electrolytic cell 124 includes hexacyano iron ions, the overall thermoelectric coefficient x of the thermoelectric element 100 may be 1.96 mV / K. Can be.

The thermoelectric element 100 described above may operate by heat of about 100 ° C. or less by using the first and second electrolytic cells 122 and 124. Thereby, the waste heat of 100 degreeC can be recycled efficiently. In addition, the movement path of electrons in the thermoelectric element 100 sequentially starts with the first lower electrode 112, and thus, the first electrolytic cell 122, the upper electrode 130, the second electrolytic cell 124, and the second lower part. Since the electrode 114 is in order, a third electrolytic cell (not shown) is disposed on the second lower electrode 114 to be spaced apart from the second electrolytic cell 124, and is spaced apart from the second lower electrode 114. An electrode (not shown) is disposed and a fourth electrolytic cell (not shown) is disposed thereon, and in the case of another upper electrode (not shown) on the third and fourth electrolytic cells, the first and second electrolytic cells are disposed. And 122 and 124 and the third and fourth electrolytic cells may be electrically connected sequentially by the upper electrodes and the lower electrodes. That is, a plurality of unit cells can be easily connected in series using the thermoelectric element 100 shown in FIG. 1 as a unit cell. When the unit cell is defined as including one upper electrode and two lower electrodes, two unit cells may be continuously connected in a structure sharing one lower electrode. On the contrary, when defined as including one lower electrode and two upper electrodes, two unit cells may be continuously connected in a structure sharing one upper electrode.

In the case of including at least two or more unit cells, a case where the electrolytic cells included in the unit cells are electrically connected alternately and electrically between the positive and negative electrolytic cell by the lower electrode and the upper electrode, It can be said that the cells are connected in series. In this case, two of the lower electrodes may be respectively connected to the positive electrode terminal and the negative electrode terminal, and the physical arrangement of the lower electrodes and the upper electrodes is not limited, and the plurality of first electrolytic cells 122 and the plurality of second electrolysiss are not limited. Cells 124 may be connected alternately.

Hereinafter, various structures of thermoelectric elements including a plurality of unit cells, a series connection of unit cells, and a method of manufacturing the same will be described in detail with reference to FIGS. 2 to 12 as a unit cell. This will be described.

2 is a perspective view illustrating a thermoelectric device according to an exemplary embodiment of the present invention.

Referring to FIG. 2, the thermoelectric element 601 includes a plurality of lower electrodes 210, a plurality of first electrolytic cells 410, and a plurality of second electrolytic cells 420 formed on the lower substrate 200. And a plurality of upper electrodes 510 (see FIG. 3) formed on the upper substrate 500. In this case, the thermoelectric element 601 further includes electrolyte channels 410 and 420 (see FIG. 5). The thermoelectric element 601 may further include the barrier rib structure 300.

The lower electrodes 210 form m × n matrices in two different directions on the lower substrate 200 (in this case, m and n are each independently one or more natural numbers except that m and n are simultaneously 1). Can be arranged). For example, n are spaced apart from each other in a line along the first direction D1 of the thermoelectric elements 601 of the lower electrodes 210, and the second direction D2 intersects with the first direction D1. M may be arranged in a line apart from each other. The first direction D1 may be a direction perpendicular to the second direction D2.

Similarly, the upper electrodes 510 are arranged on the upper substrate 500 in a matrix form of m × n, and are arranged to overlap the two lower electrodes 210 of one upper electrode 510. .

The first electrolytic cell 410 and the second electrolytic cell 420 are alternately arranged along the first direction D1 and the second direction D2. Accordingly, the first electrolytic cell 410 and the second electrolytic cell 420 are alternately arranged in the first direction D1, and the first electrolytic cell 410 and the second electrolysis are also arranged in the second direction D2. The cells 420 are alternately placed.

The first electrolytic cells 410 are disposed on one side of the first direction D1 and the other side opposite to the first direction D1 based on one of the second electrolytic cells 420. In addition, the first electrolytic cells 410 may be disposed on one side of the second direction D2 and the other side opposite to the second direction D2 based on any one of the second electrolytic cells 420. . Accordingly, two electrolyte cells 410 and 420 including different kinds of electrolytes are disposed on one lower electrode 210. A unit structure includes a structure in which one first electrolytic cell 410 and one second electrolytic cell 420 are disposed on one lower electrode 210.

In this case, the first electrolytic cell 410 disposed in the first column of the first row group may be a dummy cell, and the second electrolytic cell 420 disposed in the first column of the mth row group may be a dummy cell. These dummy cells may be omitted. In the m × n matrix form according to the present invention, not only a structure including such dummy cells but also a structure including not including m × n cells as numbers but excluding them.

Meanwhile, two different electrolytic cells 410 and 420 are disposed on one upper electrode 510. The first electrolytic cell 410 corresponds to the first electrolytic cell 122 described with reference to FIG. 1, and the second electrolytic cell 420 corresponds to the second electrolytic cell 124 described with reference to FIG. 1, each of which is substantially Duplicate detailed description is omitted since it is the same.

The partition structure 300 is disposed between the lower substrate 200 and the upper substrate 500, and serves to spatially separate the electrolytic cells 410 and 420. At the same time, the barrier rib structure 300 further includes electrolyte flow path parts 320 and 330 forming the electrolyte channels 410 and 420, which will be described later with reference to FIG. 5.

The barrier rib structure 300 includes openings 312 corresponding to each of the electrolytic cells 410 and 420, and the electrolyte cells 410 and 420 may be separated from each other by the partition wall forming the openings 312. Can be. The partition structure 300 may have openings 312 having a matrix shape of m × n. The height of the barrier rib of the barrier rib structure 300 may be constant. Alternatively, the height of the partition wall portion corresponding to the lower electrodes 210 in the partition structure 300 may be higher than the height of the partition wall portions disposed on the lower electrodes 210.

3 is a cross-sectional view of the thermoelectric element illustrated in FIG. 2.

Referring to FIG. 3 together with FIG. 2, the unit cell UC of the thermoelectric element 601 includes two lower electrodes 210, a first electrolytic cell 410, a second electrolytic cell 420, and one upper part. Electrode 510.

In contrast, the unit cell UC may be defined as one lower electrode 210, a first electrolytic cell 410, a second electrolytic cell 420, and two upper electrodes 510.

FIG. 4 is a plan view illustrating electrical connection between unit cells of the thermoelectric element illustrated in FIG. 2.

Referring to FIG. 4 together with FIGS. 2 and 3, unit cells UC adjacent to each other share the lower electrode 210, and thus may be connected to each other. On the contrary, when the unit cell UC is defined as one lower electrode 210, a first electrolytic cell 410, a second electrolytic cell 420, and two upper electrodes 510, unit cells adjacent to each other ( UC) may be connected to each other because they share the upper electrode 510. The term “adjacently disposed” refers to a first direction D1, an opposite direction of the first direction D1, a second direction D2, or an opposite direction of the second direction D2 about one unit cell UC. It means the case arranged in the direction.

Hereinafter, in the matrix of the m × n array, the nth column refers to the last column, the mth row refers to the last row in the matrix array, and the xth row refers to any one of the first to mth rows. The column y refers to any one column from the first column to the nth column. At this time, m, n, x and y each independently represent a natural number.

In detail, the first row group includes the first electrolytic cells 410 arranged from the first column to the nth column, which are the first column, in a row along the first direction D1 in the lower substrate 200. In this case, the first row group is arranged in the second direction D2 in order of the second row group, the third row group, and so on, up to the m-th row group, which is the last row group. Similarly, the first row group includes second electrolytic cells 420 arranged in a line along the first direction D1, and even the m row group in the order of the second row group, the third row group, and the like. The same applies. For example, in the first row group, the first column is the first electrolytic cell 410 and the second column is the second electrolytic cell 420, and in the second row group, the first column is the second electrolytic cell 420. And the second column may be the first electrolytic cell 410. However, in the first row group, the first second electrolytic cell 420 is the second electrolytic cell 420 in the second column, and in the second row group, the first first electrolytic cell 410 is the first electrolytic cell in the second column. Cell 410. The same description applies to the following description of the matrix arrangement.

In one row, both ends of the upper electrode 510 are disposed to overlap each of the ends of the two lower electrodes 210.

Between the rows and the rows, the outermost electrolytic cells, for example, the electrolytic cells of the nth column, which is the last column of the first row, which is the first row disposed at the first edge of the thermoelectric element 601, are opposite thereto. The electrolytic cells of the nth column, which is the last column of the second row disposed at the first edge, may be connected by one upper electrode 510. In this case, two electrolytic cells connected by one upper electrode 510 are different electrolytic cells, that is, a first electrolytic cell 410 having a positive thermoelectric coefficient and a second electrolytic cell having a negative thermoelectric coefficient ( 420). In addition, the first column of the first column of the first row of the second row disposed on the second edge facing the first edge and the first column of the first column of the third row disposed on the second edge facing the first edge Electrolytic cells may be connected by one upper electrode 510. In this manner, the unit cells UC of the thermoelectric element 601 may be connected in series as a whole.

When the electrolytic cell disposed at the first edge of the first row in the xth row group is the first electrolytic cell 410, the electrolytic cell disposed at the first edge of the first row in the x + 1 row group is second It may be an electrolytic cell 420. In contrast, when the electrolytic cell disposed at the first edge of the first row in the xth row group is the second electrolytic cell 420, the electrolytic cell disposed at the first edge of the first row in the x + 1 row group May be the first electrolytic cell 410.

In some cases, the lower electrode 210 or the upper electrode 510 disposed at any one of the first edge, the second edge, the third edge connecting the third edge, and the fourth edge facing the third edge may be external. It may be connected to the wiring connected with.

5 is an enlarged partial plan view of the thermoelectric element of FIG. 4.

In FIG. 5, the first and second electrolytic cells 410 and 420 of the x th row group and the x + 1 th row group are partially enlarged among the thermoelectric elements 601 of FIG. 4. The two electrolytic cells 410 and 420 have a structure connected to the electrolyte channels 411 and 421.

Referring to FIG. 5, each of the first electrolytic cells 410 is connected to a first electrolyte channel 411 whose both ends are defined as an inlet and an outlet. One first electrolytic cell 410 is connected to one first electrolyte channel 411. In this case, the inlet and outlet of the first electrolyte channel 411 are sealed. The plurality of first electrolyte channels 411 are physically and electrically separated from each other. The first electrolyte cells 410 and the first electrolyte channels 411 are filled with a first electrolyte solution including an electrolyte having a positive thermoelectric coefficient in which a reduction reaction occurs due to a temperature rise.

In addition, each of the second electrolytic cells 420 is connected to a second electrolyte channel 421 whose both ends are defined as an inlet and an outlet. One first electrolytic cell 420 is connected to one second electrolyte channel 421. In this case, the inlet and outlet of the second electrolyte channel 421 are sealed. The plurality of second electrolyte channels 421 are also physically and electrically separated from each other, as well as physically and electrically separated from the first electrolyte channels 411. The second electrolyte cells 420 and the second electrolyte channels 421 are filled with a second electrolyte solution including an electrolyte having a negative thermoelectric coefficient in which an oxidation reaction occurs due to a temperature rise.

FIG. 6 is a graph illustrating a change in open voltage according to the number of unit cells in the thermoelectric element illustrated in FIG. 2.

Referring to FIG. 6 together with FIG. 4, the thermoelectric coefficients of the thermoelectric elements 601 described with reference to FIGS. 2 to 5 may be [thermoelectric coefficient × N] mV / K of a unit cell. Here, N may be the number (integer) of the unit cells UC, and the number of the unit cells UC may be substantially the same as the number of the upper electrodes 510. In the thermoelectric element 601, the output voltage of one unit cell UC may be expressed by Equation 2 below.

[Equation 2]

Output voltage = thermoelectric coefficient of thermoelectric element × ΔT

In Equation 2, ΔT represents the temperature difference between the lower electrode and the upper electrode.

The graph shown in FIG. 6 is a graph in which a thermoelectric element substantially the same as the thermoelectric element 601 described in FIGS. 2 to 5 is manufactured and its open voltage is measured. In fact, the number and opening of the unit cells UC are actually shown. It can be seen that the voltage is in substantial proportional relationship.

FIG. 7 is a cross-sectional view for describing a method of manufacturing the thermoelectric element illustrated in FIG. 2.

Referring to FIG. 7, lower electrodes 210 are formed on the lower substrate 200, and the partition structure 300 is disposed thereon.

In detail, the lower electrodes 210 may be formed by depositing a metal layer on the lower substrate 200 and patterning the metal layer using a photolithography process. Alternatively, the lower electrodes 210 may be formed by printing a conductive material.

The barrier rib structure 300 is disposed on the lower substrate 200 on which the lower electrodes 210 are formed. At this time, the partition portion of the partition structure 300 has the same thickness (Hw). The plurality of openings 312 may include a first opening OP1 that is filled with a first electrolyte solution and becomes a first electrolyte cell 410, and a second opening OP2 that is filled with a second electrolyte solution and becomes a second electrolyte cell 420. ) Can be separated. Each of the plurality of first openings OP1 may be connected to the plurality of first electrolyte flow path parts 320 in a one-to-one correspondence, and each of the plurality of second openings OP2 may be connected to the plurality of second electrolyte flow path parts 330. It is connected in a one-to-one correspondence. At this time, "one-to-one correspondence" means that one electrolytic cell is connected to one electrolyte flow path part.

Subsequently, upper electrodes 510 are formed on the upper substrate 500, and the upper substrate 500 on which the upper electrodes 510 are formed is assembled with the lower substrate 200 and the barrier rib structure 300. At this time, the upper and lower portions of the barrier rib structure 300 are partially inserted into the upper electrodes 510 and the lower electrodes 210 by pressing the upper substrate 500 on which the upper electrodes 510 are formed, such as “A”. It can have a structure.

Due to the assembly of the lower substrate 200, the barrier rib structure 300, and the upper substrate 400 as shown in FIG. 7, the structure is closed in the vertical direction. On the other hand, in the left and right directions, the first and second electrolyte flow path parts 320 and 330 formed in the barrier rib structure 300 are opened. In this case, the injection hole and the discharge hole of each of the first and second electrolyte flow path parts 320 and 330 have an open state unlike that of FIG. 5.

In the state where the lower substrate 200, the barrier rib structure 300 and the upper substrate 400 are assembled, the first electrolyte solution and the second electrolyte solution are injected into the first and second electrolyte flow path parts 320 and 330, respectively. .

FIG. 8 is a plan view illustrating a method of manufacturing the thermoelectric element illustrated in FIG. 2.

Referring to FIG. 8, a first electrolyte solution and a second electrolyte solution are injected into each of the first and second electrolyte flow path parts 320 and 330. The structure of the first and second electrolyte flow path parts 320 and 330 is substantially the same as that of the first and second electrolyte channels 411 and 412. At this time, the first electrolyte solution is collectively supplied from the first supply part PV1, and injection holes of all the first electrolyte flow path parts 320 are connected to the first supply part PV1. In addition, the second electrolyte solution is collectively supplied from the second supply part PV2, and the injection holes of all the second electrolyte flow path parts 330 are connected to the second supply part PV2.

When each of the first and second electrolyte flow path parts 320 and 330 is connected to the first and second supply parts PV1 and PV2, the first electrolyte solution of the first supply part PV1 is first electrolyte by capillary action. The first opening OP1 is reached along the flow paths 320 to fill the first opening OP1. While the first electrolyte solution fills the first opening OP1, the outlets of the first electrolyte flow path parts 320 are sealed before being discharged to the outlets of the first electrolyte flow path parts 320, and the first supply part PV is closed. After removal, the injection holes of the first electrolyte flow path parts 320 are also sealed. In the same manner, the inlet of the second electrolyte flow path parts 330 is connected to the second supply part PV2, the second openings OP2 are filled with the second electrolyte solution, and the outlets are sealed, and then the second supply part PV2 is closed. By removing and sealing the injection holes, a structure such as the thermoelectric element 601 described with reference to FIG. 5 may be formed.

9 is a plan view illustrating a thermoelectric device according to another exemplary embodiment of the present invention.

The thermoelectric element 602 illustrated in FIG. 9 is substantially the same as the thermoelectric element 601 described with reference to FIGS. 2 through 6 except that the first and second electrolyte channels 412 and 422 each form a single channel. same. That is, the thermoelectric element 602 illustrated in FIG. 9 is the same as the thermoelectric element 601 described with reference to FIGS. 2 to 6 except for the structure of the electrolyte flow path portion formed in the barrier rib structure 300. Therefore, overlapping detailed description will be omitted and the differences will be mainly described.

Referring to FIG. 9 along with FIGS. 2 to 4, the thermoelectric element 602 may be formed together with the lower electrodes 210, the upper electrodes 510, and the first and second electrolytic cells 410 and 420. First and second electrolyte channels 412 and 422.

The first electrolyte channel 412 is a single channel, and the plurality of first electrolyte cells 410 are all connected to one first electrolyte channel 412. That is, a plurality of first electrolytic cells 410 are connected between the inlet and outlet of the first electrolyte channel 412. At this time, the inlet and outlet of the first electrolyte channel 412 are sealed.

In addition, the second electrolyte channel 422 is also a single channel, and a plurality of second electrolyte cells 420 are connected to one second electrolyte channel 422. That is, a plurality of second electrolytic cells 420 are connected between the inlet and outlet of the second electrolyte channel 422. At this time, the inlet and outlet of the second electrolyte channel 422 are sealed.

The first electrolyte channel 412 sequentially connects the first electrolytic cells 410 of the xth row group arranged in a line in the first direction D1, and connects the first electrolyte channels 410 in the second direction D2 of the xth row group. The first electrolytic cells 410 of the arranged x + 1 row group are sequentially connected in a direction opposite to the first direction D1. In this case, the xth row group and the x + 1th row group may be connected by connecting the first first electrolysis cells 410 with each other or the last first electrolysis cells 410 with each other in the row group. As a result, the entire first electrolytic cells 410 may be connected in series. That is, the first electrolytic cell 410 of the first column, which is the first column of the xth row group, is connected to the first electrolyte 410 of the second column, which is the second column of the x-1st row group, or the last of the xth row group. By connecting the first electrolytic cell 410 of the mth column, which is a column, and the first electrolyte 410 of the m-1th column of the x-1th row group, the first electrolytic cell 410 may be connected in series.

In addition, the second electrolyte channel 422 sequentially connects the second electrolytic cells 420 of the xth row group arranged in a row in the first direction D1, and the second direction D2 of the xth row group. ) Connects the second electrolytic cells 420 of the x + 1 row group in the opposite direction to the first direction D1. In this case, the x th row group and the x + 1 th row group may be connected by connecting the first second electrolytic cells 420 in the row group or the last second electrolytic cells 420 in the row group with each other. Accordingly, the entire second electrolytic cells 420 may be connected in series. That is, the first electrolytic cell 420 of the first column, which is the first column of the xth row group, is connected to the first electrolyte 420 of the second column, which is the second column of the x + 1 row group, or the last of the xth row group. By connecting the first electrolytic cell 410 of the mth column, which is a column, and the first electrolyte 410 of the m−1th column of the x + 1th row group, the whole may be connected in series.

The first electrolyte channel 412 and the second electrolyte channel 422 are designed so as not to interfere with each other, and the first electrolyte cells 410 and the second electrolyte cells 420 should be designed so as not to interfere with each other. In this case, the size of each of the first electrolytic cells 410 is preferably at least 10 times the size of the first electrolyte channel 412. In other words, it is preferable that the size of the first electrolyte channel 412 is equal to or less than 1/10 of the size of each of the first electrolyte cells 410. Although the first electrolytic cells 410 are connected to each other by the first electrolyte channel 412 which is a single channel, the first electrolytic cells 410 should be separated from each other. Since these have physically / electrically connected structures, problems may occur in the operation of the thermoelectric element 602. Therefore, in order to prevent this, the size of the first electrolyte channel 412 is preferably designed to be 1/10 or less of the size of each of the first electrolytic cells 410. For example, when the length of one side of each of the first electrolytic cells 410 is 500 μm, the width of the first electrolyte channel 412 may be up to 50 μm.

Similarly, it is preferable to set the size of the second electrolyte channel 414 to a size less than 1/10 of the size of each of the second electrolytic cells 420. In other words. The size of each of the second electrolytic cells 420 may be at least 10 times the size of the second electrolyte channel 422.

The design of the first and second electrolyte channels 412 and 422 shown in FIG. 9 is shown for illustrative purposes only, and as described above, there is no interference with the first and second electrolytic cells 410 and 420. It can be designed in various ways. Since the design of the first and second electrolyte channels 412, 422 is determined by the shape of the first and second electrolyte flow path portions of the partition structure 300, the first and second electrolyte flow paths of the partition structure 400 are defined. This can be achieved by forming the parts in the same shape as the first and second electrolyte channels 412 and 422 as shown in FIG. 9.

FIG. 10 is a plan view illustrating a method of manufacturing the thermoelectric element of FIG. 9.

The manufacturing method of the thermoelectric element 602 illustrated in FIG. 9 is substantially the same as that described with reference to FIGS. 7 and 8. However, the shapes of the first and second electrolyte flow path portions of the barrier rib structure 300 may have the shapes shown in FIG. 10, unlike those described with reference to FIG. 8.

In a state where the lower substrate 200 having the lower electrodes 210 formed thereon, the barrier rib structure 300, and the upper substrate 400 having the upper electrodes 410 assembled thereon, a plurality of first openings OP1 are seriesed. When the injection hole of the first electrolyte flow path portion 340 connected to the first supply portion PV1 supplies the first electrolyte solution, the first electrolyte solution sequentially fills the first openings OP1 by capillary action. And move. In this case, the first electrolyte solution is supplied to the first electrolyte flow path part 340 in the discharge hole of the first electrolyte flow path part 340.

In addition, when the injection hole of the second electrolyte flow path portion 350 connecting the plurality of second openings OP2 in series is connected to the second supply portion PV2 for supplying the second electrolyte solution, the second electrolyte may be caused by capillary action. The solution is sequentially moved while filling the second openings OP2. In this case, the second electrolyte solution is supplied to the second electrolyte flow path part 350 in an open state of the outlet of the second electrolyte flow path part 350.

After all the first and second openings OP1 and OP2 are filled to form the first and second electrolytic cells 410 and 420, the outlets of the first and second electrolyte flow path parts 340 and 350 are sealed. After removing the first and second supply parts PV1 and PV2, the injection holes thereof are also sealed. Accordingly, the thermoelectric element 602 described in FIG. 9 can be manufactured.

11 is a plan view illustrating a thermoelectric device according to yet another exemplary embodiment of the present invention.

The thermoelectric element 603 illustrated in FIG. 11 is substantially the same as the thermoelectric element 601 described with reference to FIGS. 2 to 6 except that a plurality of first and second electrolyte channels 412 and 422 are included. Do. That is, the thermoelectric element 603 illustrated in FIG. 11 is the same as the thermoelectric element 601 described with reference to FIGS. 2 to 6 except for the structure of the electrolyte flow path portion formed in the barrier rib structure 300. Therefore, overlapping detailed description will be omitted and the differences will be mainly described.

Referring to FIG. 11 along with FIGS. 2 to 4, the thermoelectric element 603 may be formed together with the lower electrodes 210, the upper electrodes 510, and the first and second electrolytic cells 410 and 420. First and second electrolyte channels 412 and 422.

The first electrolytic cells 410 and the second electrolytic cells 420 are alternately arranged in the first direction D1 and the second direction D2. In this case, each of the plurality of first electrolyte channels 412 is configured as a second electrolytic cell 410 of the y th column group and one first electrolytic cell 410 of the y + 1 th column group. Are connected to each other in the direction D2. However, the plurality of first electrolyte channels 412 are separated from each other independently, and each includes a sealed inlet and outlet.

In addition, each of the plurality of second electrolyte channels 422 may include a second electrolytic cell 420 of the y th column group and a second electrolytic cell 420 of the y + 1 th column group. Are connected to each other in the direction D2. In this case, the plurality of second electrolyte channels 422 are independently separated from each other, and each includes a sealed inlet and an outlet.

Specifically, any one of the first electrolyte channels 412 may include the first electrolytic cell 410 in the y th column of the x th row group and the first electrolytic cell 410 in the y + 1 th column of the x + 1 th row group. And one of the second electrolyte channels 422 is connected to the second electrolytic cell 420 of the y th column of the x th row group and the second electrolytic cell of the y + 1 th column of the x + 1 th row group 420 may be connected. In this case, the second electrolytic cell 420 of the nth column of the first row group is connected to a second electrolyte channel (not shown) alone, and the first electrolytic cell 410 of the first column of the mth row group is independent It may be connected to the first electrolyte channel (not shown). The first and second electrolyte channels alone may be omitted.

The thermoelectric element 603 having the structure described with reference to FIG. 11 is electrolyzed in the thermoelectric element 602 of FIG. 9 while reducing the area to be secured in order to form the electrolyte channel relative to the thermoelectric element 601 of FIG. 5. Interference / interference by electrolyte channels between cells can be minimized. That is, a structure such as the thermoelectric element 603 of FIG. 11 may form an electrolyte channel without considering such points as the size limitation of the electrolytic cell and the electrolyte channel in the thermoelectric element 602 of FIG. The thermoelectric element 603 can be manufactured easily and simply.

FIG. 12 is a plan view illustrating a method of manufacturing the thermoelectric element of FIG. 11.

The manufacturing method of the thermoelectric element 603 illustrated in FIG. 11 is substantially the same as that described with reference to FIGS. 7 and 8. However, the shapes of the first and second electrolyte flow path portions of the barrier rib structure 300 may have the shapes shown in FIG. 12, unlike those described with reference to FIG. 8.

The plurality of first openings OP1 are connected when the lower substrate 200 on which the lower electrodes 210 are formed, the barrier rib structure 300, and the upper substrate 400 on which the upper electrodes 410 are formed are assembled. Injection holes of the plurality of second electrolyte flow path parts 370 connecting the injection holes of the plurality of first electrolyte flow path parts 360 and the plurality of second openings OP2 may be the third supply part PV3 and the fourth supply part. (PV4) can be connected. Each of the third and fourth supply parts PV3 and PV4 supplies a first electrolyte solution and a second electrolyte solution. In some cases, the third and fourth supply units PV3 and PV4 may be integrated into one or divided into multiple units.

When the injection holes of the plurality of first electrolyte flow path parts 360 and the injection holes of the plurality of second electrolyte flow path parts 370 are connected to the third and fourth supply parts PV3 and PV4, the first electrolyte may be formed by capillary action. The solution and the second electrolyte solution may move to fill the first openings OP1 and the second openings OP2.

The first and second electrolyte solutions are supplied to the outlets of the first electrolyte channel parts 360 and the second electrolyte channel part 370 in an open state, but all of the first and second openings OP1 and OP2 are filled. After the first and second electrolytic cells 410 and 420 are formed to seal the outlets of the first and second electrolyte flow path parts 360 and 370, and the third and fourth supply parts PV3 and PV4 are sealed. After removal, their inlets are also sealed. Accordingly, the thermoelectric element 603 described in FIG. 11 can be manufactured.

As described above with reference to FIGS. 2 to 12, a thermoelectric element including a unit cell capable of operating by living waste heat of 100 ° C. or less may improve output voltage and power productivity. The thermoelectric element may be applied to an electronic device to operate by heat generated by the driving of the electronic device to generate electric power, and to be easily used in a window or a greenhouse of an automobile.

Hereinafter, an apparatus to which the above-described thermoelectric element is applied will be described with reference to FIGS. 13 to 17.

13 is a cross-sectional view illustrating an apparatus including a thermoelectric device according to an exemplary embodiment of the present invention.

Referring to FIG. 13, the apparatus 701 including the thermoelectric element includes a display unit 710, a power supply unit 720, and a battery cover 730. For example, the device 701 may be a portable small device such as a mobile phone, and the display unit 710 may include a display panel and a backlight assembly. The battery cover 730 may fix the power supply unit 720 to the display unit 710 and protect the power supply unit 720.

The power supply unit 720 is disposed between the display unit 710 and the battery cover 730 and is electrically connected to the display unit 710 to supply power to the display panel and the backlight assembly. Includes a battery 722 formed.

Thermoelectric element 724 is the thermoelectric element described above in accordance with the present invention. In this case, the thermoelectric elements 724 may be thermoelectric elements 601, 602, and 603 including at least two or more unit cells UC described with reference to FIGS. 2 to 11. Accordingly, detailed descriptions thereof will not be repeated. The lower substrate 200 described above is disposed on one surface of the thermoelectric element 724 directly contacting the battery 722, and the back cover 730 and the upper substrate 500 are provided to face each other. The thermoelectric element 724 may be connected to the battery 722 to generate power by operating by heat generated when the power supply unit 722 is driven or heat generated by the display unit 710.

FIG. 14 is a diagram for describing a connection relationship between a thermoelectric element and a battery in FIG. 13.

Referring to FIG. 14 together with FIG. 13, a thermoelectric element 724 is connected with a battery 722, where a positive electrode of the battery 722 is connected with a positive terminal of the thermoelectric element 724 and a negative electrode of the battery 722 is thermoelectric. It may be connected to the negative terminal of the device 724. In this case, the positive electrode terminal is connected to the outermost one lower electrode among the lower electrodes of the thermoelectric element 724, and the negative electrode terminal is connected to the outermost one lower electrode among the lower electrodes of the thermoelectric element 724. It may be an external terminal of 724.

In this case, the thermoelectric element 724 may be connected to the capacitor CAP. That is, the thermoelectric element 724 generates power using waste heat, and the capacitor CAP connected thereto stores the power generated by the thermoelectric element 724. The capacitor CAP is connected to the battery 722 to receive power from the capacitor CAP as needed by the battery 722. Although not shown in the drawings, a switch for controlling the on / off of the capacitor CAP may be further provided.

The lower substrate 200 of the thermoelectric element 732 may be omitted, and the lower electrodes 210 may be directly formed on one surface of the battery 722. Accordingly, the thermoelectric element 732 and the battery 722 may have an integrated structure.

15 to 17 are diagrams for describing an apparatus including a thermoelectric device according to an exemplary embodiment of the present invention.

Referring to FIG. 15, an apparatus 702 including a thermoelectric device according to an exemplary embodiment of the present invention includes a display unit 710, a battery 722, and a cover unit 734. The display unit 710 and the battery 722 are substantially the same as described with reference to FIG. 13. Therefore, redundant descriptions are omitted.

The cover unit 734 includes a battery cover 730 on which a thermoelectric element 732 is formed. In this case, the thermoelectric element 732 may be integrally formed with the battery cover 730. In this case, the lower substrate 200 of the thermoelectric element 732 may be disposed to face the battery 722, and the upper substrate 500 may be formed on the battery cover 730. In contrast, the upper substrate 500 may be omitted, and the upper electrodes 510 may be directly formed on the battery cover 730 such that the thermoelectric element 732 and the battery cover 730 may have an integrated structure. The capacitor connected to the thermoelectric element 732 may be formed on the battery cover 730. Alternatively, the capacitor may be physically separated to be connected to the battery 722 on the battery 722 side, and the capacitor and the battery 722 may be electrically connected when the battery 722 and the cover unit 734 are coupled to each other. It may include a terminal.

In this case, the battery 722 and the thermoelectric element 732 are electrically connected through the connection terminals 724a, 724b, 736a, and 736b. That is, the connection terminals 736a and 736b are formed in the battery 722, and the thermoelectric element 732 also contacts the connection terminals 736a and 736b at positions corresponding to the connection terminals 736a and 736b. Capable terminals 724a and 724b may be formed so that the battery 722 and the thermoelectric element 732 may be electrically connected when the cover unit 734 is combined with the battery 722.

Referring to FIG. 16, an apparatus including a thermoelectric device according to the present invention may be a window for an automotive sunroof. That is, by connecting the thermoelectric element described with reference to FIGS. 2 to 12 to the window for the vehicle sunroof, the power generated by the thermoelectric element may be used to drive the vehicle.

The electrodes 210 and 510 and the substrates 200 and 500 of the thermoelectric element connected to the window for the automotive sunroof may be formed of a transparent or translucent material, and the partition structure 300 may also be formed of a transparent or translucent material. . The lower substrate 200 of the thermoelectric element may be attached to the window for the vehicle sunroof, and the upper substrate 500 may face the lower substrate 200 to face the interior of the vehicle. That is, the thermoelectric element may operate by increasing the temperature of the lower substrate 200 and the lower electrodes 210 by solar heat. Alternatively, the lower substrate 200 may be omitted, and the lower electrodes 210 may be formed directly on the window of the vehicle.

Meanwhile, a thermoelectric element coupled to a window for an automotive sunroof may be connected to a capacitor to store power generated by solar heat in the capacitor.

As described above, the electrodes 210 and 510 and the substrates 200 and 500 constituting the thermoelectric element are formed of a material capable of transmitting at least 80% of visible light, so that the front, rear and / or front of the vehicle Thermoelectric elements can also be applied to the side windows.

Referring to FIG. 17, an apparatus including a thermoelectric device according to the present invention may be a greenhouse window. That is, by applying the thermoelectric element described with reference to FIGS. 2 to 12 to the greenhouse window, it is possible to convert the thermal energy into electrical energy by using the indoor and outdoor temperature difference generated by sunlight. The obtained electrical energy can be used for facility cooling / heating and lighting.

Although not illustrated in the drawings, the thermoelectric device according to the present invention may be applied to the windows of a house / commercial building in substantially the same manner as the apparatus described with reference to FIGS. 16 and 17.

Claims (26)

1. A plurality of lower electrodes;

   A first electrolyte disposed on each of the lower electrodes, the first electrolyte having a positive thermoelectric coefficient in which a reduction reaction occurs due to an increase in temperature of the lower electrode, and an inlet and an outlet are disposed at both ends and accommodate the first electrolyte; First electrolytic cells connected to the first electrolyte channel;

   A second electrolyte disposed on one lower electrode and spaced apart from the first electrolytic cell, the second electrolyte having a negative thermoelectric coefficient at which an oxidation reaction occurs due to a temperature rise of the lower electrode, and an inlet and an outlet are disposed at both ends and Second electrolyte cells connected to a second electrolyte channel containing a second electrolyte; And

   It includes a plurality of upper electrodes disposed on the first and second electrolytic cells to be connected to the first electrolytic cell and the second electrolytic cells disposed on the different lower electrodes,

   Thermoelectric elements.
2. The method of claim 1,

   The first electrolytic cells are connected in a one-to-one correspondence to a plurality of first electrolyte channels, each of which is independent of each other having an inlet and an outlet,

   The second electrolytic cells may be connected in a one-to-one correspondence with a plurality of second electrolyte channels each having an inlet and an outlet, which are independent of each other.

   Thermoelectric elements.
3. The method of claim 1,

   The first electrolytic cells are connected in series between the inlet and outlet of the first electrolyte channel,

   The second electrolytic cells are characterized in that connected in series between the inlet and outlet of the second electrolyte channel,

   Thermoelectric elements.
4. The method of claim 3,

   The first electrolytic cell and the second electrolytic cell are alternately arranged in the first direction, and the first electrolytic cell and the second electrolytic cell are alternately arranged in the second direction crossing the first direction,

   The first electrolyte channel is

   The first electrolytic cells included in the x row group (where x is a natural number), which is any row group arranged in a row, are sequentially connected in the first direction, and are arranged in the second direction of the x row group. Sequentially connecting the first electrolysis cells of the x + 1 row group in the opposite direction to the first direction, and the x th row group and the x + 1 row group are the first first electrolysis cells in the row group. Connect the last first electrolytic cells to each other or to the corresponding row group,

   The second electrolyte channel is

   The second electrolytic cells included in the xth row group, which are any row groups arranged in a row, are sequentially connected in the first direction, and the x + 1 row group arranged in the second direction of the xth row group The second electrolytic cells of are sequentially connected in a direction opposite to the first direction, and the xth row group and the x + 1 row group are the first second electrolytic cells in the row group or last in the row group. Characterized in that the second electrolytic cells are connected to each other,

   Thermoelectric elements.
5. The method of claim 1,

   The first electrolytic cell and the second electrolytic cell are alternately arranged in the first direction, and the first electrolytic cell and the second electrolytic cell are alternately arranged in the second direction crossing the first direction,

   Any one of the first electrolytic cells included in the y th column group (where y is a natural number) and any one first electrolytic cell of the y + 1 column group arranged in a row is the first electrolyte Connected to each other in the second direction by a channel, the plurality of first electrolyte channels are separated from each other independently,

   Any one of the second electrolytic cells of the y-th column group and any of the second electrolysis cells of the y + 1 column group, which is any one column group arranged in a row, is mutually connected in the second direction by a second electrolyte channel. Connected, wherein the plurality of second electrolyte channels are separated from each other independently,

   The first electrolytic cells are connected in series between the inlet and outlet of the first electrolyte channel,

   The second electrolytic cells are characterized in that connected in series between the inlet and outlet of the second electrolyte channel,

   Thermoelectric elements.
6. The method of claim 5,

   The first electrolyte channel includes the first electrolytic cell of the yth column of the xth row group (where x represents a natural number) and the y + 1 column of the x + 1 row group, which are any row groups arranged in a row. Connecting the first electrolytic cell,

   The second electrolyte channel connects the second electrolytic cell of the y th column of the x th row group, which is any one row group arranged in a row, and the second electrolytic cell of the y + 1 th column of the x + 1 th row group. Made,

   Thermoelectric elements.
7. The method of claim 6,

   The second electrolytic cell of the last column of the first row group is connected to the second electrolyte channel alone,

   The first electrolytic cell of the first column of the last row group is connected to the first electrolyte channel alone,

   Thermoelectric elements.
8. The method of claim 1,

   Redox couples are included in the first electrolytic cell is _{Fe 2 (SO 4) 3 /} FeSO 4, I - / I 3-, Np 4+ / NpO 2 +, Pu 4 + / PuO 2 2 +, CN - / is at least one selected ^{_{from, - CNO -, NO 2 -}} / NO 3 -, I - / IO 3 -, ClO 3 - / ClO 4 -, ClO - / ClO 2 - and Cl ^- / ClO

   Redox couples included in the second electrolytic cell are K ₃ Fe (CN) ₆ / K ₄ Fe (CN) ₆ , K ₃ Fe (CN) ₆ / (NH ₄ ) ₄ Fe (CN) _6, Np ^{3 +} / Np ^{4 +} , Cu ⁺ / Cu ^{2 +} , Fe ^{2 +} / Fe ^{3 +} , PuO ₂ ⁺ / PuO ₂ ^{2 +} , Pu ^{3 +} / Pu ^{4 +} , NpO ₂ ⁺ / NpO ₂ ²⁺ , Tl ⁺ / Tl ^{3 +} , NH ₄ ⁺ / N ₂ H ₅ ⁺ , NH ₄ ⁺ / NH ₃ OH ⁺ , Mn ^{2 +} / Mn ^{3 +} and Am ^{3 +} / Am ^{4 +} characterized in that at least one selected from

   Thermoelectric element.
9. The method of claim 1,

   The barrier rib structure is interposed between the lower electrodes and the upper electrodes and separates the first and second electrolytic cells.

   Openings corresponding to the first and second electrolytic cells;

   A first electrolyte flow path part connected to at least one opening in which the first electrolyte cell is disposed to form a first electrolyte channel; And

   And a second electrolyte flow path part connected to at least one opening in which the second electrolyte cell is disposed to form a second electrolyte channel.

   Thermoelectric elements.
10. The method of claim 1,

    When a temperature difference occurs between the lower electrodes and the upper electrode,

    Based on any one of the lower electrodes, electrons continuously move in the order of the lower electrode, the first electrolytic cell, the upper electrode, the second electrolytic cell, and the other lower electrode disposed adjacent to the one lower electrode. doing,

    Thermoelectric elements.
11. The method of claim 1,

    In one row, the lower electrodes and the upper electrodes are arranged in a line in the first direction,

    The upper electrodes are arranged in a second direction crossing the first direction to connect the first and second electrolytic cells in the first column of the different rows between the different rows, or the first column in the last column of the different rows. And connecting the second electrolytic cells to each other,

    Thermoelectric elements.
12. The method of claim 1,

    The first electrolyte and the second electrolyte

    Characterized in that the liquid or gel (gel) state,

    Thermoelectric element.
13. Forming a plurality of lower electrodes disposed in a matrix on a lower substrate in a first direction and a second direction crossing the first direction;

    Arranging a partition structure including a plurality of openings, a first electrolyte flow path part, and a second electrolyte flow path part on a lower substrate on which the bottom electrodes are formed, such that two openings among the plurality of openings are located at one bottom electrode; ;

    Assembling the upper substrate, on which the upper electrodes are formed, with the lower substrate and the partition structure so that two upper electrodes are disposed on one lower electrode; And

    Injecting a first electrolyte solution into the first electrolyte flow path portion to form a first electrolytic cell in the opening connected to the first electrolyte flow path portion, and injecting a second electrolyte solution into the second electrolyte flow path portion to the second electrolyte flow path portion Forming a second electrolytic cell in the opening connected to the

    Method of manufacturing a thermoelectric element.
14. The method of claim 13,

    Forming the second electrolytic cell is

    Injecting the first electrolyte solution into one end while the both ends of the first electrolyte channel part are opened;

    Injecting the second electrolyte solution into one end while the both ends of the second electrolyte flow path part are opened;

    Sealing one end and the other end of the first electrolyte flow path part in a state where the first electrolyte solution is filled in the opening connected to the first electrolyte flow path part and the first electrolyte flow path part; And

    And sealing one end and the other end of the second electrolyte flow path part in a state where the second electrolyte solution is filled in the opening connected to the second electrolyte flow path part and the second electrolyte flow path part.

    Method of manufacturing a thermoelectric element.
15. The method of claim 13,

    The openings

    First openings connected to each of a plurality of first electrolyte flow path parts independent of each other; And

    Second openings connected to a plurality of second electrolyte flow path portions independent of each other,

    The first openings and the second openings are alternately arranged in the first direction and at the same time alternately arranged in the second direction,

    Method of manufacturing a thermoelectric element.
16. The method of claim 13,

    The openings

    A plurality of first openings connected to the first electrolyte channel part; And

    A plurality of second openings connected to the second electrolyte flow path part;

    The first openings and the second openings are alternately arranged in the first direction and at the same time alternately arranged in the second direction,

    Method of manufacturing a thermoelectric element.
17. The method of claim 13,

    The barrier rib structure includes at least two first electrolyte flow path parts and at least two second electrolyte flow path parts,

    Each of the first electrolyte flow path portions connects first openings in the second direction,

    Each of the second electrolyte flow path portions connects the second openings in the second direction.

    Method of manufacturing a thermoelectric element.
18. The method of claim 17,

    Each of the first electrolyte flow path portions is independent of each other,

    Characterized in that each of the second electrolyte flow path portion is also independent of each other,

    Method of manufacturing a thermoelectric element.
19. An apparatus comprising a battery having a thermoelectric element according to any one of claims 1 to 12.
20. The method of claim 19,

    And the positive and negative terminals of the thermoelectric element are connected to the positive and negative electrodes of the battery, respectively.
21. The method of claim 19,

    And a capacitor is formed in the battery that stores the power produced by the thermoelectric element and delivers it to the battery.
22. An apparatus comprising a battery cover having a thermoelectric element according to any one of claims 1 to 12.
23. The method of claim 22,

    The thermoelectric element is

    And a positive terminal and a negative terminal in contact with the positive and negative electrodes of the battery, respectively, and electrically connected to the lower electrodes and the upper electrodes.
24. The method of claim 22,

    And a capacitor connected to the thermoelectric element to store power generated by the thermoelectric element is formed in the battery cover, and the capacitor has a terminal connected to the battery.
25. 13. The sunroof window for automobiles, wherein the thermoelectric element according to any one of claims 1 to 12 is formed.
26. A greenhouse window in which the thermoelectric element according to any one of claims 1 to 12 is formed.

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